Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/90—Compositions for taking dental impressions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

• the present invention relates to a transparent material based on addition-crosslinking polysiloxanes, which e.g. is used as an occlusal stamp for forming posterior tooth composites or as a fixation splint for brackets in orthodontics and preferably for bite registration therapy in the dental field.
• a transparent material based on addition-crosslinking polysiloxanes, which e.g. is used as an occlusal stamp for forming posterior tooth composites or as a fixation splint for brackets in orthodontics and preferably for bite registration therapy in the dental field.
• transparent materials e.g. B. by light polymerization.
• the bite registration materials mentioned as preferred in dentistry are used to fix the correct positional relationship from lower jaw to upper jaw in the mouth and to transfer this position to the model in the dental laboratory.
• Waxes and preferably elastomeric materials such as polyethers and silicones are used for this.
• Bite registration materials must meet special requirements. They should have a stable consistency and be characterized by high final hardness, low elastic deformability and minimal dimensional change.
• the material according to the invention based on addition-crosslinking silicone materials is distinguished by a high degree of transparency, which enables the dental position taken by the patient to be checked in the mouth and, if necessary, allows the bite to be corrected under visual control.
• the material can be set for a very short processing time. A processing time of only approx.
• 35 - 45 seconds reduces the risk of the patient shifting the position of the lower jaw from the position once it has been taken.
• the bite can be removed from the mouth after 2 minutes 30 seconds.
• this addition-crosslinking silicone material does not undergo any clinically relevant dimensional changes and thus gives bite registrations that are permanently stable in storage.
• the possibility of checking the model position in the bite registration is also of particular importance due to the transparency. Position shifts of the models, which leads to a time-consuming correction of the carry out finished work in the mouth, this control option, which is not available with all other opaque materials, can be determined even before the dentures are made.
• Dental impression materials based on addition-crosslinking polysiloxanes are known per se (cf. e.g. R: G. Graig, Restaurative Dental Materials, The C.V. Moosbe-Comp., St. Louis, 1980, p. 195 ff).
• compositions generally consist of a base paste containing silicone oil, filler and crosslinking agent and a catalyst paste of silicone oil, filler and catalyst.
• the base and catalyst paste are preferably mixed 1: 1 by weight or volume and applied to the jaw area to be molded using a syringe and / or impression spoon. After crosslinking by means of a polyaddition reaction, the rubber-like impression is removed from the patient's mouth and then poured out with an aqueous slurry of model plaster.
• Bite registration materials based on addition-crosslinking silicones are also known and commercially available. They are structured similarly to the above. Dental impression materials. The higher final hardness and lower elastic deformations are achieved through the use of even larger proportions of fillers. The short processing times of these materials can be set by a higher proportion of platinum catalyst. These highly filled two-component materials are opaque and give a hard and brittle rubber after the addition reaction.
• a covering matrix for light-crosslinkable fillers which consists of 6% polymethylhydro (65-70%) dimethylsiloxane copolymer and 94% vinyldimethyl end-stopped polydimethylsiloxane with a viscosity of 60,000 csk, with a mixture of 1% chloroplatinic acid complex as catalyst and 99% vinyldimethyl end-stopped polydimethylsiloxane with a viscosity of 60,000 csk was used. It is taught to mix the base paste and catalyst paste with a spatula and to apply the material obtained to the tooth surface to be restored and the surrounding area.
• QM resins are characterized in that, as explained in W. Noll, Chemistry and Technology of Silicones, Verlag Chemie, Weinheim, 2nd edition, 1964, page 3, the tetrafunctional SiO4 / 2 as Q units and as M -Building blocks contain the monofunctional R3SiO1 / 2, where R can be vinyl, methyl, ethyl, phenyl.
• R can be vinyl, methyl, ethyl, phenyl.
• the trifunctional RSiO3 / 2 and the bifunctional R2SiO2 / 2 with the same meaning for R as above can also be present as T units.
• the content according to the invention of 0-10% by weight of QM resin, preferably 0-5% by weight of QM resin in the entire silicone system brings about a significant improvement in the crosslinking density and thus a higher tensile strength and hardness of the elastomeric product.
• Component b) of the above formulation is contained in the base paste, component c) in the catalyst paste.
• Base and catalyst paste of the bite registration material according to the invention are characterized by high transparency and good storage stability with regard to viscosity; the bite registers produced from it have hardness, high transparency and tear resistance with little elastic deformation.
• the organopolysiloxane a) is a known vinyl end-stopped polydimethylsiloxane, the viscosity of which is in the range from 100 to 100,000 mPa ⁇ s, preferably 200 to 10,000 mPa ⁇ s at 20 ° C (silicone oils).
• organohydrogenpolysiloxanes which act as crosslinkers are b) are also known polydimethylsiloxanes which have hydrogen atoms on at least two silicon atoms in the molecule.
• the catalyst c) is a platinum complex which was produced from hexachloroplatinic acid. These connections are also known per se.
• the dyes d which may be used to differentiate between base and catalyst paste and for mixing control, should be finely dispersed in order not to disturb the transparency.
• organic color pigments are preferred. According to DE-A-35 44 619, solutions of dyes in isoparaffins such as 2,2,4,4,6,6,8-heptamethylnonane (C16H34) or 2,2,4,4,6,6,8, 8,10-nonamethylundecane (C20H42) can be used.
• the compounds e) to be used according to the invention are, for example, as described in DE-A-25 35 324, from a precipitated or pyrogenically prepared silica with a specific surface area of more than 50 m 2 / g according to BET and a trimethylsilyl- and / or vinyl-terminated polydimethylsiloxane with a viscosity preferably between 100 and 200,000 mPa ⁇ s at 20 ° C using modifiers, for example hexarmethyldisilazane, tetramethyldivinyldisilazane produced.
• R2 can be a substituted or unsubstituted hydrocarbon radical and is preferably selected from alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl, i-propyl, amyl, or aryl radicals, such as tolyl, xylyl, Ethylphenyl, or aralkyl radicals, such as benzyl, phenylethyl or halogen-substituted alkyl or aryl radicals, such as chloromethyl, 3,3,3-trifluoropropyl, chlorophenyl, tetrachlorophenyl, difluorophenyl and alkenyl radicals, such as vinyl, allyl.
• R2 also represents cyanoalkyl, cycloalkyl and cycloalken
• R1 has the same meaning as R2, but can also represent a vinyl group.
• R 1 and R 2 may be present in one molecule of component 1).
• the size of the number m is decisive for the viscosity of the linear polyorganosiloxane and is chosen so that the viscosity of the linear polyorganosiloxane is preferably between 100 mPa ⁇ s and 2 ⁇ 105 mPa ⁇ s at 20 ° C.
• Component 1) can also consist of mixtures of polymers with different sizes of the number m.
• Component 2 is a commercially available, highly disperse, active filler with a BET surface area of at least 50 m2 / g.
• Substances such as TiO2, Al2O3, ZnO or preferably pyrogenically obtained or wet-precipitated silica are suitable.
• the manufacturing process and the chemical nature of the filler play no role in the use according to the invention. It is only important that it is a filler with a BET surface area in the order of magnitude specified. It is also advantageous that no filler modified during or after its production is used.
• suitable fillers are pyrogenically obtained or wet-precipitated silica which are sold under the trade names AEROSIL® (Degussa), CABOSIL® (Cabot), HDK® (Wacker-Chemie), pyrogenically obtained aluminum oxide or titanium dioxide under the name ALUMINUM OXIDE O® or TITANDIOXID P 25® (Degussa) or ZINKOXID AKTIV® (BAYER AG) can be offered.
• AEROSIL® Degussa
• CABOSIL® Cabot
• HDK® Widecker-Chemie
• pyrogenically obtained aluminum oxide or titanium dioxide under the name ALUMINUM OXIDE O® or TITANDIOXID P 25® (Degussa) or ZINKOXID AKTIV® (BAYER AG) can be offered.
• radical R is a methyl radical and the radical X represents the group NY, where Y is preferably a hydrogen atom.
• the modifier is added in an amount of 1-50, preferably 3-20 parts by weight.
• water is added to the mixture of component 1) and the modifier before adding the highly dispersed active filler in an amount of 0.1 to 10 parts by weight, preferably 2 to 6 parts by weight.
• the presence of water favors the reaction between the modifier and the highly disperse filler.
• the water contributes to an accelerated, uniform distribution of the filler in the presence of the modifier.
• the highly dispersed active filler is incorporated at room temperature or only at a slightly elevated temperature.
• the familiarization is not critical and no special precautionary measures need to be taken. It is expedient not to add the highly disperse active filler to the mixture of constituent 1), the modifier and water all at once, but in portions, so that the amount of highly disperse active filler added in each case is wetted and incorporated in a short time.
• the distribution of the highly disperse active filler in the mixture of component 1), the modifier and water can be made with commercially available, suitable devices, preferably with so-called Z kneaders or planetary stirrers.
• the amount of the highly dispersed active filler to be incorporated depends on the desired consistency of the mixture and, in the case of mixtures in which constituent 1) contains radicals R 1 or R 2, which are accessible to a cross-linking reaction at room temperature with corresponding cross-linking substances, the required mechanical properties of the cross-linked Gums.
• the mixture consisting of component 1), the modifier, water and filler is preferably subjected to a short-term mechanical stress (e.g. excess pressure, pressure between rollers, kneading stress) in such a way that the mixture is 10 minutes to 2 Remains in the sealed mixer for hours.
• a short-term mechanical stress e.g. excess pressure, pressure between rollers, kneading stress
• excess modifier and water are removed in such a way that either a vacuum is applied or the mixing unit is opened and vented at elevated temperature until excess modifier and water have practically completely evaporated.
• the temperature is preferably increased and a vacuum is applied at the same time.
• the QM resins g) optionally used according to the invention are known per se. Their manufacture is e.g. For example, described in U.S. Patents 2,676,182, 2,857,356 and 3,527,659.
• the ratio of the sum of R3SiO 1/2 - and EtO 1/2 units to the SiO 4/2 units should be less than 2.5 and is limited by the optically clear solubility of the QM resins in the vinyl endstopped Polydimethylsiloxanes, or by the optical clarity of the end products.
• the QM resins can also contain small amounts of R2SiO and RSiO 3/2 units without this interfering with the use according to the invention, but the R2SiO and RSiO 3/2 units should not exceed 20 mol% by weight .
• a kneader 270 parts of vinyl-stopped polydimethylsiloxane with a viscosity of 10 Pa ⁇ s and 310 parts of vinyl-stopped polydimethylsiloxane with a viscosity of 65 Pa ⁇ s at 20 ° C are mixed with 68 parts of hexamethyldisilazane and 12 parts of tetramethyldivinyldisilazane and 50 parts of water and then mixed with 330 Parts of a fumed silica with a BET surface area of 300 m 2 / g kneaded to a homogeneous mass.
• the mixture was first at 130 ° C heated and stirred for 1.5 hours in a closed kneader and then freed from volatile constituents for 1 hour at 160 ° C. under vacuum. After cooling, the compound is diluted with 120 parts of vinyl-terminated polydimethylsiloxane with a viscosity of 10 Pa ⁇ s at 20 ° C. with stirring.
• the base paste of a bite registration material was prepared in a kneader by mixing 70.0 parts of compound from Example 1, 6.6 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa ⁇ s at 20 ° C and 23.4 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
• the associated catalyst paste was obtained by mixing 69.2 parts of compounds from Example 1, 0.8 parts of a complex of platinum and divinyltetramethyldisiloxane as a catalyst, 10 parts of the short-chain vinyl-terminated polydimethylsiloxane with an SiVi content of 1.8 mmol / g and one Viscosity of 10 mPa ⁇ s at 20 ° C and 20 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
• Both pastes had a viscosity of approx. 50,000 mPa ⁇ s at 20 ° C and were transparent. They were each filled into a chamber of a double cartridge and pressed with a double piston gun through an attached static mixer and mixed with it. 30 seconds after leaving the static mixer, the processing time was ended by increasing the viscosity as a result of the onset of the addition reaction; after a further 2 minutes, the mixture was crosslinked to form a transparent rubber with good tear strength and a hardness of 69 Shore A. This bite registration material was assessed well in the application test.
• a bite registration material base paste is produced in a kneader by mixing 67.5 parts of compound from Example 1, 24.0 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa s at 20 ° C and 8.5 parts of a vinyl end-stopped Polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
• the associated catalyst paste was prepared in the same way by mixing 70.0 parts of compound from Example 1, 15.2 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C., 9.0 parts of a short-chain, vinyl-terminated polydimethylsiloxane a SiVi content of 1.8 mmol / g and a viscosity of 10 mPa ⁇ s at 20 ° C, 5.0 parts of a QM resin of the formula [Si O 4/2 ] [Me Vi SiO 1/2 ] 1.0 [Et O 1/2 ] 0.4 with a viscosity of 800 mPa ⁇ s at 20 ° C and 0.8 parts of a complex of platinum and divinyltetramethyldisiloxane as a catalyst.
• the viscosity of the base paste was approx. 47,000 mPa ⁇ s and the catalyst paste was approx. 52,000 mPa ⁇ s at 20 ° C. Both pastes were transparent.
• the pastes mixed as described above had a processing time of 45 seconds and a setting time of 2 minutes 45 seconds.
• the cross-linked rubber was transparent, had a high tear strength and a hardness of 78 Shore A. The application-related assessment of this bite registration material was very good.
• the base paste of a bite registration material was prepared in a kneader by mixing 70.0 parts of compound from Example 1, 5.8 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa ⁇ s at 20 ° C and 24.2 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
• the corresponding catalyst paste was prepared in a kneader by mixing 76.4 parts of the compound from Example 1, 0.6 part of a complex of platinum and divinyltetramethyldisiloxane as a catalyst and 24.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s 20 ° C.
• the base paste had a viscosity of approx. 48,000 mPa ⁇ s, the catalyst paste approx. 58,000 mPa ⁇ s at 20 ° C. Both pastes were transparent.
• the pastes in one A double cartridge filled and pressed through the attached static mixer using a double piston gun resulted in a processing time of 40 seconds and a setting time of 2 minutes 30 seconds.
• the cross-linked rubber had good transparency and tear resistance, but only had a Shore A hardness of 50 and was very flexible.
• the application test assessed the material as unsuitable due to its low hardness and high flexibility.
• the base paste of a bite registration material was produced in a kneader by mixing 10.0 parts of the compound from Example 1, 5.8 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa ⁇ s at 20 ° C, 24.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 1,000 mPa ⁇ s at 20 ° C, 59.8 parts of fine cristobalite flour with an average grain size of approx. 4 ⁇ m and 0.4 parts of an organic color pigment.
• the associated catalyst paste was obtained by mixing 16.5 parts of the compound from Example 1, 23.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 1,000 mPas at 20 ° C., 0.5 part of a complex of platinum and divinyltetramethyldisiloxane and 60, 0 parts og Fine cristobalite flour.
• the base paste had a viscosity of approx. 54,000 mPa ⁇ s and the catalyst paste of approx. 60,000 mPa ⁇ s at 20 ° C, both pastes were opaque.
• the pastes mixed as described above had a processing time of 45 seconds and a setting time of 2 minutes 45 seconds.
• the cross-linked rubber had a low tear strength, a hardness of 77 Shore A and was not transparent. This bite registration material was assessed as moderately suitable in the application test because of its opacity and slight brittleness.
• the mixture has a processing time of 20 seconds and a curing time of 1 minute.
• the crosslinked product obtained was not sufficiently transparent due to the numerous enclosed gas bubbles.
• the components were mixed with a double-piston pistol in a static mixer.
• the processing time was 22 seconds
• the crosslinking time was 1 minute.
• the hardness (Shore A) was only 18, the product was transparent but did not have sufficient tensile strength.
• Example 7 was modified by producing the base paste from 96% by weight of the vinyl end-stopped polydimethylsiloxane and 4% by weight of the crosslinker according to Example 6.
• the composition of the catalyst was the same.
• the processing time was 30 seconds, the crosslinking time 1 minute and 20 seconds, the hardness (Shore A) was 19.
• the product obtained had sufficient transparency, but the tensile strength was completely inadequate.
• the mixture described above was modified again by preparing the base paste from 94% by weight of the same vinyldimethyl end-stopped polydimethylsiloxane and 6% by weight of the crosslinker from 90% by weight of dimethyl and 10% by weight of methylhydrogen siloxane.
• the catalyst paste was prepared from 97% by weight vinyldimethyl end-stopped polydimethylsiloxane as described above and 3% by weight platinum catalyst.
• the processing time was 2 minutes and 30 seconds, the cross-linking time was approx. 6 minutes.
• the hardness (Shore A) was 18, the transparency of the product was sufficient, but the tensile strength of the material was again below that Minimum application requirements.
• the viscosity of the mixture before crosslinking was too low for dental applications.
• the mixture would flow from the teeth into the patient's jaw and throat area when attempting to apply it.
• Example 3 was modified by using a catalyst component made from 2.5% by weight of the QM resin instead of 5% by weight of the same.
• the processing time was 45 seconds, the cross-linking time 3 minutes.
• the hardness (Shore A) was 73, the product was sufficiently transparent and of high tensile strength.
• compositions according to the invention clearly show the superiority of the compositions according to the invention over those of the prior art.
• the latter have a completely insufficient tensile strength, which means that they cannot be removed from the teeth to be treated without damage. Therefore, compositions of this type cannot be used to produce a so-called occlusal stamp of the area to be supplied before the supply of a cavity with a light-curing composite.

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• 1991
  • 1991-07-05 DE DE4122310A patent/DE4122310A1/de not_active Withdrawn
• 1992
  • 1992-06-22 ES ES92110471T patent/ES2095355T3/es not_active Expired - Lifetime
  • 1992-06-22 DK DK92110471.7T patent/DK0522341T3/da active
  • 1992-06-22 AT AT92110471T patent/ATE146211T1/de not_active IP Right Cessation
  • 1992-06-22 EP EP92110471A patent/EP0522341B1/fr not_active Expired - Lifetime
  • 1992-06-22 DE DE59207651T patent/DE59207651D1/de not_active Expired - Fee Related
  • 1992-07-01 JP JP04195881A patent/JP3122238B2/ja not_active Expired - Lifetime
  • 1992-07-03 IE IE922184A patent/IE80529B1/en not_active IP Right Cessation
• 1993
  • 1993-11-22 US US08/156,660 patent/US5403885A/en not_active Expired - Lifetime
• 1996
  • 1996-12-12 GR GR960403416T patent/GR3022016T3/el unknown

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